EP0120466B2 - Heat-curable coating composition and its use - Google Patents

Heat-curable coating composition and its use Download PDF

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Publication number
EP0120466B2
EP0120466B2 EP84103141A EP84103141A EP0120466B2 EP 0120466 B2 EP0120466 B2 EP 0120466B2 EP 84103141 A EP84103141 A EP 84103141A EP 84103141 A EP84103141 A EP 84103141A EP 0120466 B2 EP0120466 B2 EP 0120466B2
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European Patent Office
Prior art keywords
coating agent
primary
component
amino groups
groups
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German (de)
French (fr)
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EP0120466B1 (en
EP0120466A1 (en
Inventor
Werner Dr. Loch
Eberhard. Dr. Schupp
Rolf Dr. Osterloh
Klaas Dr. Ahlers
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BASF Farben und Fasern AG
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BASF Lacke und Farben AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C08G85/004—Modification of polymers by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C09D5/4496—Cathodic paints characterised by the nature of the curing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/901—Electrodepositable compositions

Definitions

  • the invention relates to heat-curable coating compositions which cure without acid catalysis and without the release of formaldehyde, and the use thereof.
  • Aminoplast hardeners e.g. Urea, melamine or benzoguanamine resins are known as conventional crosslinkers. They contain methylol or methylol ether groups. Their effectiveness is linked to the presence of acidic groups in the binder or at least to the absence of basic groups, which not only limits their possible uses, but can also lead to corrosion due to the acid remaining in the film on metallic substrates; in addition, formaldehyde is always split off during the crosslinking reaction, sometimes in considerable quantities.
  • EP 12 463 and EP 40 867 describe heat-curable coating compositions which crosslink via an interesterification reaction without acid catalysis and without splitting off formaldehyde.
  • organically dissolved paints, powder coatings and cathodic electro-dipping paints In order to achieve sufficient crosslinking of the coating films at curing temperatures ⁇ 200 ° C, the crosslinker must have a sufficient number of ⁇ -hydroxyester groups, which, as is known, can be implemented much more easily than normal ester groups.
  • ⁇ -hydroxy esters are sensitive to hydrolysis. This leads to bath stability problems if the coating agents are to be used as binders for cathodic electrocoating materials.
  • the object of the present invention was to overcome these disadvantages, i.e. to provide a new type of thermosetting coating composition which gives organically dissolved stoving enamels or powder enamels which cure in the absence of acid without the release of formaldehyde.
  • Another object of the present invention was to provide heat-curable coating compositions which, after neutralization with an acid, can be diluted with water, are stable as an aqueous dispersion over a period of ⁇ 3 months, can be deposited on a metallic substrate serving as a cathode and at temperatures of ⁇ 200 ° C can be burned into coatings with excellent corrosion protection.
  • EP-A-119 769 describes a coating composition based on a thermosetting resin which, as a resin binder, contains a film-forming resin with a ⁇ -hydroxycarbamate group which is at most substituted by an alkyl substituent.
  • EP-A-102 556 describes a curable mixture which contains a ⁇ -hydroxyurethane.
  • the structural components described in this document lead to ⁇ -hydroxyurethanes with at most one alkyl substituent.
  • US Pat. No. 4,122,069 discloses the use of certain polyethers which contain hydroxylalkyl carbamate groups at the chain ends (e.g. addition products of 2 mol of ethylene carbonate with 1 mol of polyether diamine of molecular weight 2000 to 3000) for improving the adhesion of epoxy-based adhesives which Cure room temperature, known.
  • these systems still contain intact epoxy groups via which the crosslinking takes place, while according to the invention, inter alia, Epoxy / amine adducts, which no longer contain free epoxy groups, are crosslinked with the hydroxyalkyl carbamates (8) at elevated temperature.
  • Component (A) can preferably be a polyester, a polyacrylate or in particular a polyaddition product carrying nitrogen-based groups, the groupings of the formula which are bonded to aromatic rings contains, a reaction product of phenolic Mannich bases and epoxy resins or a reaction product of one or more aromatic or aliphatic epoxy resins and one or more primary or secondary amines.
  • the present invention also relates to the use of the coating compositions according to the invention as a component of organically dissolved stoving lacquers and for powder coating.
  • Component (A) can be selected from a wide variety of compound classes. It is important that they have a medium molecular weight M n has between 500 and 10,000 and has on average at least two OH and / or primary and / or secondary amino groups.
  • Component (A) should preferably have a resin-like character.
  • suitable materials are polyesters, alkyd resins, polyethers, polyacrylate resins, polyurethanes. Polyurethane ureas, epoxy resins and their reaction products with alcohols, mercaptans or amines.
  • Another suitable class of compounds are polydiene resins or oils, e.g. Polybutadiene oils. These can e.g. introduce OH groups by adding mercaptoethanol to some of the double bonds. A further possibility of introducing OH groups is the reaction with maleic anhydride and subsequent reaction with OH-containing amines such as ethanolamine or diethanolamine. The required derivatization can also be carried out by epoxidation of the polybutadiene oils with peracids and subsequent reaction with amines.
  • Suitable polyesters are, for example, those with an average molecular weight M n from 500 to 10,000 and a hydroxyl number from 25 to 400, obtainable from aliphatic and / or aromatic dicarboxylic acids with 4 to 10 carbon atoms, for example succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid or terephthalic acid their derivatives and aliphatic diols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propanediol, butanediol, hexanediol, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester and optionally higher alcohols, such as trimethylolpropane, glycerol, erythritol, trieth
  • Suitable alkyd resins have a similar structure, only they contain up to 40% by weight of one or more monocarboxylic acids, e.g. Fatty acids. Alkyd resins which contain glycidyl esters of branched carboxylic acids can also be used.
  • Suitable polyethers are e.g. aliphatic or araliphatic polyethers, which are obtained by reacting di- and / or polyhydric alcohols with different amounts of ethylene and / or propylene oxide.
  • Suitable polyacrylates are OH group-containing polyacrylates with a hydroxyl number of 25 to 500. These should have an acid number ⁇ 25, preferably ⁇ 10 and a K value according to Fikentscher (3% in acetone) from 10 to 40, preferably from 12 to 25 and can contain the following monomers:
  • Suitable polyurethanes are:
  • OH-group-containing polyurethanes with a hydroxyl number of 25 to 600 from aliphatic and / or aromatic diisocyanates which for example consist of tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, naphthylene diisocyanate, 4,4'-diphenyl ether or diisocyanate, and optionally diisocyanate
  • aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, propanediol, butanediol, hexanediol, neopentyl glycol or hydroxypivalic acid neo-pentylglycol esters and optionally higher alcohols, such as trimethylolpropane, glycerol, pentaerythritol or
  • Suitable polyurethane ureas are corresponding reaction products of the polyisocyanates mentioned and the aliphatic diols mentioned or higher alcohols in a mixture with aliphatic diamines, such as, for example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, neopentanediamine, hexamethylenediamine, diaminocyclohexane, diaminodicyclohexane, diaminodiaminodicyclohexane, 3,3-dimethyl-4,4'-diamine-dicyclohexylmethane, 4,9-dioxadodecane-1,12-diamine, and optionally higher-value amines, such as trisaminoethyl-amine or 1,1,1-trisaminopropoxymethyl-propane.
  • aliphatic diamines such as, for example, ethylenediamine, propylened
  • Pure polyureas for example from the polyisocyanates mentioned and the polyamines mentioned, can also be used as component (A) in the coating compositions according to the invention.
  • Suitable epoxy resins are, for example, glycidyl ethers, such as those produced from 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin. These epoxy resins can be modified further, for example by reaction with polyfunctional alcohols or SH compounds. Examples of such polyfunctional alcohols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol. If elasticization is desired, long-chain polyfunctional alcohols or mercaptans can also be used. Are the polyfunctional alcohols or mercaptans in larger than equivalent Amounts used in relation to the epoxy groups present result in products with terminal OH or SH groups.
  • Reaction products of epoxy resins with primary or secondary amines can also be used as component (A).
  • the reaction with hydroxyl-containing amines such as e.g. Ethanolamine, methylethanolamine and diethanolamine.
  • component (A) which contain sufficient amounts of amino groups in order to become water-soluble or water-dispersible after protonation with acids
  • component (B) water-dispersible stoving enamel binders
  • component (B) in particular those which are intended for the cathodic Electrocoating
  • the above-mentioned reaction products of epoxy resins with primary or secondary amines can be used for this purpose.
  • carrier resins proposed for cathodic electrocoating can also be used as component (A) in the coating compositions according to the invention, for example the reaction products of phenolic Mannich bases with epoxy resins according to DE-PS 2419179, the reaction products of chain-extended epoxy resins with secondary amines according to US-PS 4104147 , Reaction products of (meth) acrylamidomethylated phenols, amines and epoxy resins according to EP 27 641, EP 41 619 etc; it is only important that they have an average molecular weight M n of 500 to 10,000 and on average have at least two OH and / or primary and / or secondary amino groups per molecule.
  • component (A) contains only OH groups and no primary and / or secondary amino groups
  • component (A) contains only OH groups and no primary and / or secondary amino groups
  • One way of obtaining products with primary and secondary amino groups suitable as component (A) is to react excess primary diamines with epoxy resins and then separate the excess amine at elevated temperature and reduced pressure.
  • Suitable diamines are, in particular, those having 2 to 6 carbon atoms, for example ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, neopentanediamine and hexamethylenediamine.
  • the reaction products can be chain-extended with dicarboxylic acids, for example with sebacic acid or dimeric fatty acid.
  • the ratio of dicarboxylic acid to epoxy / amine adduct allows the desired molecular weight to be set, e.g. B. you can use 1 mol of dimeric fatty acid on two molecules of epoxy / amine adduct.
  • a further possibility of producing suitable products with primary amino groups as component (A) is the conversion of epoxy resins with secondary amines which contain blocked primary amino groups.
  • examples of such amines are the diketimine of diethylenetriamine, the ketimine of aminoethylethanolamine, the ketimine of diethylenetriamine, the ketimine of aminoethylethanolamine, the ketimine of N-methylethylenediamine and the ketimine of N-aminoethylpiperazine.
  • the ketimines can be easily derived from the free amines and a ketone, e.g. Prepare methyl isobutyl ketone by removing water. When reacting with epoxy resins, only the secondary amino group reacts, then the ketimine can be split off by simply adding water, the free primary amino group regressing.
  • these products can also be elasticized by chain extension.
  • Component (A) is contained in the binder mixture according to the invention in an amount of 1 to 90, preferably 50 to 85% by weight, in particular 65 to 80% by weight.
  • Component (B) is present in the coating compositions according to the invention in amounts of 10 to 99% by weight, preferably 15 to 50% by weight, in particular 20 to 35% by weight.
  • polyamine ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane, neopentanediamine, Hexamethylene diamine, 4,9-dioxadodecane diamine-1,12, 4,4'-diaminodicyclohexylamine, 4,4'-bis (amino-ethoxy) -2,2-diphenylpropane, 4,4'-bis (aminopropoxy) -2.2 -diphenylpropane, tris (aminoethyl) amine, 1,1,1-tris-aminopropoxymethylpropane, ⁇ , ⁇ -bis (aminomethyl) -n-butylamine, tetrakis (aminomethyl) methane, tris (
  • suitable polyamines (a) include amidamines which are obtained, for example, by reacting polycarboxylic acids, e.g. Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid and the like, or their anhydrides with excess diamines, such as, for example, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane, neopentanediamine, hexamethylenediamine and the like at elevated temperatures under water cleavage after removing the excess diamine by distillation in vacuo.
  • polycarboxylic acids e.g. Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid and the like
  • excess diamines such as, for example, propylenediamine, 1,4-diaminobutane, 1,5-diaminopen
  • oligomeric or polymeric polyamines with molecular weights up to 3000 can also be used.
  • examples of such polyamines are diamines which can be prepared by reductive cyanoethylation of polyols such as polytetrahydrofuran.
  • Such products contain terminal primary amino groups in the form of aminopropoxy groups. They can still contain more or less large amounts of OH groups.
  • oligomeric or polymeric polyamines with molecular weights up to 3000 which are suitable as component (a) are epoxy / amine adducts which contain on average at least two primary amino groups per molecule and also OH groups. They can be manufactured essentially in two ways.
  • the first consists in the reaction of epoxy resins with excess primary diamines and the subsequent separation of the excess diamine at elevated temperature and reduced pressure.
  • Suitable epoxy resins are, for example, polyglycidyl ethers of polyphenols, such as, for example, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, bis - (2-hydroxynaphthyl) methane and the like, which are prepared by etherification of the polyphenols mentioned with epichlorohydrin in the presence of alkali, polyglycidyl ethers of polyhydric alcohols, which are reacted by appropriate reaction of epichlorohydrin with polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, propanediol -1,2, propanediol-1,3, pentanediol-1,5, 2,2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethylolpropane, pentaerythritol and the like can be obtained, N, N-diglycid
  • Elasticization by means of long-chain dis-amines such as, for example, dimer fatty acid bis- [2- (2-hydroxyethylamino) ethyl] amide, which are also used in smaller than equivalent amounts, is possible.
  • elastification and amine conversion can be carried out synchronously.
  • Suitable diamines for this purpose are especially those with 2 to 6 carbon atoms, e.g. Ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, neopentanediamine and hexamethylenediamine.
  • the reaction products can, if no previous elasticization has taken place, be chain-extended with dicarboxylic acids, e.g. with sebacic acid or dimeric fatty acid.
  • the ratio of dicarboxylic acid to epoxy / amine adduct can be used to set the desired molecular weight, e.g. one can use 1 mol of dimeric fatty acid on two molecules of epoxy / amine adduct.
  • the second way consists in the reaction of the epoxy resins mentioned with secondary amines which contain blocked primary amino groups.
  • examples of such amines are the diketimine of diethylenetriamine, the ketimine of aminoethylethanolamine, the ketimine of N-aminoethylpiperazine and the ketimine of N-methylethylenediamine.
  • the ketimines can be easily derived from the free amines and a ketone, e.g. Prepare methyl isobutyl ketone by removing water.
  • the ketimine can then be cleaved by simply adding water, the free primary amino group regressing.
  • these products can also be elasticized by chain extension.
  • Cyclic carbonic acid esters suitable as component (b) are, for example, isobutylene carbonate, butylene-2,3-carbonate. They can be obtained in a simple manner from the corresponding epoxides by reaction with carbon dioxide.
  • component (a) takes place either in bulk or in suitable solvents, such as water, alcohols, ethers, esters, ketones, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons.
  • suitable solvents such as water, alcohols, ethers, esters, ketones, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons.
  • the reactants should be at least largely soluble in the solvents or solvent mixtures used, and the latter themselves should not contain primary or secondary amino groups or mercapto groups, which can also react with the cyclic carbonic acid esters.
  • the preferred solvents are water, alcohols and ether alcohols, such as methanol, ethanol, propanols, butanols and monoethers of diols, for example ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol with the monoalkanols mentioned first.
  • ether alcohols such as methanol, ethanol, propanols, butanols and monoethers of diols, for example ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol with the monoalkanols mentioned first.
  • Components (a) and (b) are generally reacted at temperatures from 0 to 80 ° C., preferably 15 to 40 ° C.
  • the reactants are mixed at room temperature and left to stand until the required amine number decrease has taken place. Response times range from about 1 to about 48 hours.
  • Components (A) and (B) are mixed to produce the coating compositions according to the invention.
  • components with low viscosity this can take place in bulk, where appropriate heating to temperatures of up to 130 ° C.
  • Products with higher viscosity are dissolved in organic solvents before mixing.
  • Common solvents such as alcohols, ketones, esters, ethers, hydrocarbons etc. can be used.
  • the coating compositions according to the invention can be processed together with soluble dyes, fillers, pigments or the like to form organically dissolved paints by customary methods. These can additionally contain additives customary in coating technology, such as leveling agents, defoamers, wetting agents, curing catalysts and, in minor amounts, additional crosslinking agents and other binders.
  • the stoving temperatures are generally between 130 and 200 ° C, preferably between 150 and 180 ° C, the stoving times are 20 to 30 minutes, provided that curing catalysts are used.
  • Tin compounds such as dibutyltin dilaurate, dibutyltin oxide, tin acetate and the like are preferred as hardening catalysts.
  • Lead compounds such as lead naphthenate, lead octoate or lead acetate are also suitable.
  • the additions are made in amounts of 0.5 to 4% by weight, preferably 1 to 2.5% by weight, based on the paint binder.
  • solid components (A) and (B), the softening products of which should be> 60 ° C for reasons of blocking resistance, are ground dry and with conventional additives such as pigments, fillers and in minor amounts hardening catalysts and leveling agents, for example based on polyacrylate.
  • the mixtures are then melt-homogenized at temperatures around 100 ° C (eg in an extruder). After cooling the extrudates These are thoroughly ground at room temperature and the powder coating components below a particle size of approx. 90 ⁇ m are separated off by sieving. The parts above are used again for further grinding.
  • the powder coatings are applied in the customary manner by electrostatic powder spraying.
  • the stoving conditions are the same as for conventional paints.
  • powder coatings described above are subjected to a subsequent wet grinding in water until a particle size of ⁇ 10 to 20 ⁇ m is obtained, stable aqueous powder suspensions are obtained which can be applied and baked like the conventional coatings described above.
  • epoxy / amine adducts are used as component (A) in the coating compositions according to the invention, they are water-soluble or dispersible after protonation with acids. They can therefore be used as binders for cathodically depositable electrocoat materials.
  • Electrodeposition paints are produced by customary methods. Inorganic and organic acids such as formic acid, acetic acid, lactic acid or phosphoric acid are used as neutralizing agents, carboxylic acids being preferred. Their quantities are such that Bad p values of 6.5 to 8.0, preferably 7.0 to 7.5, result, so that corrosion of the systems is avoided.
  • the baths can also contain other customary additives, such as pigments, fillers, leveling agents, wetting agents, surface-active agents and, in minor amounts, additional other paint binders and / or crosslinking agents.
  • the coating compositions according to the invention can thus be used for coating any electrically conductive substrates, such as iron, which may have been chemically pretreated, e.g. can be phosphated, use aluminum, copper and the like.
  • the deposition voltages are generally 50 to 500 V, preferably 150 to 350 V.
  • baking conditions are required, as have already been described in the description of the conventional systems.
  • Example 1 describes the preparation of an organic dissolved stoving lacquer, which contains a polyacrylate resin as component (A).
  • feed I consisting of 520 parts of butanediol monoacrylate, 610 parts of tert-butyl acrylate, 660 parts of n-butyl acrylate, 200 parts of methyl methacrylate and 10 parts of acrylic acid
  • feed II consisting of 540 parts of acetic acid -n-butyl ester and 50 parts of azo-bis-isobutyronitrile, added dropwise within 6 hours.
  • the resulting 60% solution of the polyacrylate resin in n-butyl acetate has a Fikentscher K value of 24 (3% in dimethylformamide), an acid number of 1 mg KOH / g and an OH number of 98 mg KOH / g on.
  • a mixture of 214 parts of iron oxide yellow, 107 parts of 1,9-anthrapyrimidine-2-carboxylic acid anthraquinolylamide and 107 is obtained in a mixture of 1000 parts of the acrylate resin in Example 1a), 514 parts of the reaction product according to Example 1b), 17 parts of dibutyltin dilaurate and 329 parts of ethylene glycol monoethyl ether
  • Parts of titanium dioxide are pasted and ground in a stirrer mill with 2100 parts of glass beads (diameter 2 mm) until a granularity according to DIN 53 203 of ⁇ 10 ⁇ m is reached. After removing the grinding media, a 55% yellow varnish is created.
  • This lacquer is diluted with a little n-butyl acetate to a run-out time of 30 seconds in a DIN 4 beaker, sprayed onto steel sheets and, after flashing off for 5 minutes at room temperature, baked at 160 ° C. for 20 minutes. After being rubbed back and forth 50 times with a cotton ball soaked in methyl isobutyl ketone, the baked films show no attack.
  • Pendulum hardness according to König 120 sec.
  • Example 2 describes the preparation of an organically dissolved stoving lacquer which contains a polyester, especially an alkyd resin, as component (A).
  • the lacquer is diluted with a little xylene to a run-out time in DIN 4 cups of 30 seconds, sprayed onto steel sheets and, after flashing off for 5 minutes at room temperature, baked at 180 ° C. for 20 minutes.
  • the burned-in films show no attack after rubbing back and forth 50 times with a cotton ball soaked in methyl isobutyl ketone.
  • Pendulum hardness according to König 164 sec.
  • Example 3 describes the production of an organically dissolved stoving lacquer which contains an epoxy / amine adduct as component (A) and is suitable, for example, as a filler for automotive coating.
  • Höpler viscosity (50% in ethylene glycol monobutyl ether at 20 ° C): 4700 mPa.s
  • Pendulum hardness according to König 178 sec

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  • Polyurethanes Or Polyureas (AREA)

Abstract

Heat-curable surface-coating agents useful in organically dissolved baking finishes, for powder coating and for cathodic electrocoating contain, as a binder, a mixture of a polyadduct, polycondensate or other polymer which has an average molecular weight &upbar& Mn of from 500 to 10,000 and, per molecule, on average two or more OH and/or NH groups, and a reaction product of a polyamine which contains on average two or more primary amino groups per molecule and a cyclic carbonic acid ester of the formula (I) <IMAGE> (I) where R1, R2, R3 and R4 each are hydrogen, methyl or ethyl.

Description

Die Erfindung betrifft hitzehärtbare Überzugsmittel, welche ohne Säurekatalyse und ohne Formaldehydabspaltung aushärten, und deren Verwendung.The invention relates to heat-curable coating compositions which cure without acid catalysis and without the release of formaldehyde, and the use thereof.

Aminoplasthärter, z.B. Harnstoff-, Melamin- oder Benzoguanaminharze sind als übliche Vernetzer bekannt. Sie enthalten Methylol- bzw. Methylolethergruppen. Ihre Wirksamkeit ist an das Vorhandensein von sauren Gruppen im Bindemittel oder zumindest an das Fehlen von basischen Gruppen gebunden, was nicht nur ihre Einsatzmöglichkeiten beschränkt, sondern durch die im Film verbleibende Säure auf metallischen Substraten auch zu Korrosion führen kann; ausserdem wird bei der Vernetzungsreaktion stets Formaldehyd abgespalten, z.T. in erheblichen Mengen.Aminoplast hardeners, e.g. Urea, melamine or benzoguanamine resins are known as conventional crosslinkers. They contain methylol or methylol ether groups. Their effectiveness is linked to the presence of acidic groups in the binder or at least to the absence of basic groups, which not only limits their possible uses, but can also lead to corrosion due to the acid remaining in the film on metallic substrates; in addition, formaldehyde is always split off during the crosslinking reaction, sometimes in considerable quantities.

Im EP 12 463 und EP 40 867 sind hitzehärtbare Überzugsmittel beschrieben, welche ohne Säurekatalyse und ohne Formaldehydabspaltung über eine Umesterungsreaktion vernetzen. Als Verwendungszweck werden u.a. organisch gelöste Lacke, Pulverlacke und kathodische Elektrotauchlacke genannt. Um bei Härtungstemperaturen < 200°C eine ausreichende Vernetzung der Lackfilme zu erreichen, muss der Vernetzer über eine genügende Anzahl von β-Hydroxyestergruppierungen, die bekanntermassen wesentlich leichter umgesetzt werden können als normale Estergruppen, verfügen. β-Hydroxyester sind jedoch hydrolyseempfindlich. Dies führt zu Badstabilitätsproblemen, wenn die Überzugsmittel als Bindemittel für kathodische Elektrotauchlacke verwendet werden sollen.EP 12 463 and EP 40 867 describe heat-curable coating compositions which crosslink via an interesterification reaction without acid catalysis and without splitting off formaldehyde. Among other things, organically dissolved paints, powder coatings and cathodic electro-dipping paints. In order to achieve sufficient crosslinking of the coating films at curing temperatures <200 ° C, the crosslinker must have a sufficient number of β-hydroxyester groups, which, as is known, can be implemented much more easily than normal ester groups. However, β-hydroxy esters are sensitive to hydrolysis. This leads to bath stability problems if the coating agents are to be used as binders for cathodic electrocoating materials.

Mit der Maßgabes, daß mindestens zwei Reste für Methyl und/oder Ethyl stehen. S. AnlageWith the proviso that at least two radicals represent methyl and / or ethyl. See attached

Ein weiterer, genereller Nachteil der Überzugsmittel gemäss EP 12463 und EP 40867 besteht darin, dass durch die Vernetzungsreaktion Esterbindungen geknüpft werden, welche relativ hydrolyseempfindlich sind; dies kann sich nachteilig auf den Korrosionsschutz der Beschichtungen auswirken.Another general disadvantage of the coating compositions according to EP 12463 and EP 40867 is that the crosslinking reaction forms ester bonds which are relatively sensitive to hydrolysis; this can adversely affect the corrosion protection of the coatings.

Aufgabe der vorliegenden Erfindung war es, diese Nachteile zu beheben, d.h. eine neue Art von hitzehärtbaren Überzugsmitteln bereitzustellen, die organisch gelöste Einbrennlacke oder Pulverlacke ergeben, die in Abwesenheit von Säure ohne Formaldehydabspaltung aushärten. Eine weitere Aufgabe der vorliegenden Erfindung bestand darin, hitzehärtbare Überzugsmittel aufzuzeigen, die nach Neutralisation mit einer Säure wasserverdünnbar, über einen Zeitraum von ≧ 3 Monaten als wässerige Dispersion stabil sind, sich auf einem als Kathode dienenden metallischen Substrat abscheiden lassen und bei Temperaturen << 200°C zu Überzügen mit ausgezeichnetem Korrosionsschutz eingebrannt werden können.The object of the present invention was to overcome these disadvantages, i.e. to provide a new type of thermosetting coating composition which gives organically dissolved stoving enamels or powder enamels which cure in the absence of acid without the release of formaldehyde. Another object of the present invention was to provide heat-curable coating compositions which, after neutralization with an acid, can be diluted with water, are stable as an aqueous dispersion over a period of ≧ 3 months, can be deposited on a metallic substrate serving as a cathode and at temperatures of <200 ° C can be burned into coatings with excellent corrosion protection.

Gegenstand der vorliegenden Erfindung sind hitzehärtbare Überzugsmittel, die dadurch gekennzeichnet sind, dass sie als Bindemittel enthalten ein Gemisch aus

  • (A) 1 bis 90 Gew.% eines Polyadditions-, Polykondensations- oder Polymerisationsproduktes mit einem mittleren Molekulargewicht M n von 500 bis 10000, welches im Mittel pro Molekül mindestens zwei OH- und/oder primäre und/oder sekundäre Amino-Gruppen besitzt, und
  • (B) 99 bis 10 Gew.% eines Umsetzungsprodukts aus
  • a) mindestens einem Polyamin, das im Mittel mindestens zwei primäre Aminogruppen pro Molekül und gegebenenfalls zusätzlich Hydroxylgruppen enthält, und
  • b) 75 bis 200 Mol.%, bezogen auf die primären Aminogruppen der Komponente a) mindestens eines cyclischen Kohlensäureesters der allgemeinen Formel (I)
Figure imgb0001
 worin R¹, R², R³ und R⁴ untereinander gleich oder verschieden sind und für Wasserstoff, einen Methyl- oder einen Ethylrest stehen.The present invention relates to heat-curable coating compositions, which are characterized in that they contain a mixture of binders
  • (A) 1 to 90% by weight of a polyaddition, polycondensation or polymerization product with an average molecular weight M n from 500 to 10,000, which is at least per molecule on average has two OH and / or primary and / or secondary amino groups, and
  • (B) 99 to 10% by weight of a reaction product
  • a) at least one polyamine which contains on average at least two primary amino groups per molecule and optionally additionally hydroxyl groups, and
  • b) 75 to 200 mol%, based on the primary amino groups of component a) of at least one cyclic carbonic acid ester of the general formula (I)
Figure imgb0001
 wherein R¹, R², R³ and R⁴ are the same or different from each other and represent hydrogen, a methyl or an ethyl radical.

In der EP-A-119 769 wird eine Beschichtungsmasse beschrieben auf der Basis eines wärmehärtbaren Harzes, das als Harzbindemittel ein filmbildendes Harz enthält mit einer β-Hydroxycarbamat-Gruppe, die höchstens mit einem Alkylsubstituenten substituiert ist.EP-A-119 769 describes a coating composition based on a thermosetting resin which, as a resin binder, contains a film-forming resin with a β-hydroxycarbamate group which is at most substituted by an alkyl substituent.

In der EP-A-102 556 wird eine härtbare Mischung beschrieben, die ein β-Hydroxyurethan enthält. Die in dieser Schrift beschriebenen Aufbaukomponenten führen zu β-Hydroxyurethanen mit höchstens einem Alkylsubstituenten.EP-A-102 556 describes a curable mixture which contains a β-hydroxyurethane. The structural components described in this document lead to β-hydroxyurethanes with at most one alkyl substituent.

Aus der US-A-4 122 069 ist die Mitverwendung bestimmter Polyether, die an den Kettenenden Hydroxylalkylcarbamatgruppierungen enthalten (z. B. Additionsprodukte von 2 Mol Ethylencarbonat an 1 Mol Polyetherdiamin vom Molekulargewicht 2000 bis 3000) zur Haftungsverbesserung von Klebstoffen auf Epoxidharzbasis, die bei Raumtemperatur aushärten, bekannt. Diese Systeme enthalten jedoch noch intakte Epoxidgruppen, über die die Vernetzung erfolgt, während erfindungsgemäss u.a. Epoxid/Amin-Addukte, die keine freien Epoxidgruppen mehr enthalten, bei erhöhter Temperatur mit den Hydroxyalkylcarbamaten (8) vernetzt werden.US Pat. No. 4,122,069 discloses the use of certain polyethers which contain hydroxylalkyl carbamate groups at the chain ends (e.g. addition products of 2 mol of ethylene carbonate with 1 mol of polyether diamine of molecular weight 2000 to 3000) for improving the adhesion of epoxy-based adhesives which Cure room temperature, known. However, these systems still contain intact epoxy groups via which the crosslinking takes place, while according to the invention, inter alia, Epoxy / amine adducts, which no longer contain free epoxy groups, are crosslinked with the hydroxyalkyl carbamates (8) at elevated temperature.

Komponente (A) kann vorzugsweise ein Polyester, ein Polyacrylat oder insbesondere ein stickstoffbasische Gruppen tragendes Polyadditionsprodukt, das an aromatische Ringe gebundene Gruppierungen der Formel

Figure imgb0002
enthält, ein Umsetzungsprodukt aus phenolischen Mannichbasen und Epoxidharzen oder ein Umsetzungsprodukt aus einem oder mehreren aromatischen oder aliphatischen Epoxidharzen und einem oder mehreren primären oder sekundären Aminen sein.Component (A) can preferably be a polyester, a polyacrylate or in particular a polyaddition product carrying nitrogen-based groups, the groupings of the formula which are bonded to aromatic rings
Figure imgb0002
 contains, a reaction product of phenolic Mannich bases and epoxy resins or a reaction product of one or more aromatic or aliphatic epoxy resins and one or more primary or secondary amines.

Gegenstand der vorliegenden Erfindung ist ausserdem die Verwendung der erfindungsgemässen Überzugsmittel als Bestandteil organisch gelöster Einbrennlacke und für die Pulverlackierung.The present invention also relates to the use of the coating compositions according to the invention as a component of organically dissolved stoving lacquers and for powder coating.

Ferner sind derartige durch zumindest teilweise Neutralisation mit einer Säure wasserverdünnbare Überzugsmittel, die damit erhältlichen wässerigen Lackbader und deren Verwendung für die kathodische Elektrotauchlackierung Gegenstand der Erfindung.Furthermore, such coating compositions which are water-dilutable by at least partial neutralization with an acid, the aqueous paint baths obtainable therewith and their use for cathodic electrocoating are the subject of the invention.

Zu den Aufbaukomponenten der erfindungsgemässen Überzugsmittel ist im einzeinen folgendes zu sagen:To the structural components of the invention Coating agent can be said in detail as follows:

(A) Die Komponente (A) kann aus den verschiedensten Verbindungsklassen ausgewählt werden. Wichtig ist, dass sie ein mittleres Molekulargewicht M n zwischen 500 und 10000 aufweist und im Mittel mindestens zwei OH- und/oder primäre und/oder sekundäre Amino-Gruppen besitzt.(A) Component (A) can be selected from a wide variety of compound classes. It is important that they have a medium molecular weight M n has between 500 and 10,000 and has on average at least two OH and / or primary and / or secondary amino groups.

Bevorzugt soll die Komponente (A) einen harzartigen Charakter haben. Beispiele geeigneter Materialien sind Polyester, Alkydharze, Polyether, Polyacrylatharze, Polyurethane. Polyurethanharnstoffe, Epoxidharze und ihre Umsetzungsprodukte mit Alkoholen, Mercaptanen oder Aminen. Eine weitere geeignete Verbindungsklasse sind Polydienharze oder -öle, z.B. Polybutadienöle. In diese lassen sich z.B. durch Addition von Mercaptoethanol an einen Teil der Doppelbindungen OH-Gruppen einführen. Eine weitere Möglichkeit, OH-Gruppen einzuführen, ist die Umsetzung mit Maleinsäureanhydrid und nachfolgende Reaktion mit OH-haltigen Aminen wie Ethanolamin oder Diethanolamin. Auch durch Epoxidierung der Polybutadienöle mit Persäuren und anschliessende Umsetzung mit Aminen lässt sich die benötigte Derivatisierung durchführen.Component (A) should preferably have a resin-like character. Examples of suitable materials are polyesters, alkyd resins, polyethers, polyacrylate resins, polyurethanes. Polyurethane ureas, epoxy resins and their reaction products with alcohols, mercaptans or amines. Another suitable class of compounds are polydiene resins or oils, e.g. Polybutadiene oils. These can e.g. introduce OH groups by adding mercaptoethanol to some of the double bonds. A further possibility of introducing OH groups is the reaction with maleic anhydride and subsequent reaction with OH-containing amines such as ethanolamine or diethanolamine. The required derivatization can also be carried out by epoxidation of the polybutadiene oils with peracids and subsequent reaction with amines.

Geeignete Polyester sind z.B. solche mit einem mittleren Molekulargewicht M n von 500 bis 10000 und einer Hydroxylzahl von 25 bis 400, erhältlich aus aliphatischen und/oder aromatischer Dicarbonsäuren mit 4 bis 10 Kohlenstoffatomen, beispielsweise Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Cyclohexandicarbonsäure, Phthalsäure, Isophthalsäure oder Terephthalsäure bzw. deren Derivaten und aliphatischen Diolen, wie Ethylenglykol, Diethylenglykol, Triethylenglykol, Polyethylenglykol, Propandiol, Butandiol, Hexandiol, Neopentylglykol oder Hydroxypivalinsäureneopentylglvkolester und gegebenenfalls höherwertigen Alkoholen, wie Trimethylolpropan, Glycerin, Erythrit, Pentaerythrit, Trimethylolbenzol oder Trishydroxyethylisocyanurat.Suitable polyesters are, for example, those with an average molecular weight M n from 500 to 10,000 and a hydroxyl number from 25 to 400, obtainable from aliphatic and / or aromatic dicarboxylic acids with 4 to 10 carbon atoms, for example succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid or terephthalic acid their derivatives and aliphatic diols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propanediol, butanediol, hexanediol, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester and optionally higher alcohols, such as trimethylolpropane, glycerol, erythritol, triethylishthritol, pentethylerythritol.

Geeignete Alkydharze sind ähnlich aufgebaut, nur enthalten sie bis zu 40 Gew.% einer oder mehrerer Monocarbonsäuren, wie z.B. Fettsäuren. Auch Alkydharze, welche Glycidylester von verzweigten Carbonsäuren enthalten, können verwendet werden.Suitable alkyd resins have a similar structure, only they contain up to 40% by weight of one or more monocarboxylic acids, e.g. Fatty acids. Alkyd resins which contain glycidyl esters of branched carboxylic acids can also be used.

Geeignete Polyether sind z.B. aliphatische oder araliphatische Polyether, welche durch Umsetzung von zwei- und/oder mehrwertigen Alkoholen, mit verschiedenen Mengen an Ethylen- und/oder Propylenoxid erhalten werden.Suitable polyethers are e.g. aliphatic or araliphatic polyethers, which are obtained by reacting di- and / or polyhydric alcohols with different amounts of ethylene and / or propylene oxide.

Geeignete Polyacrylate sind OH-gruppenhaltige Polyacrylate mit einer Hydroxylzahl von 25 bis 500. Diese sollten eine Säurezahl < 25, bevorzugt < 10 und einen K-Wert nach Fikentscher (3%ig in Aceton) von 10 bis 40, vorzugsweise von 12 bis 25 aufweisen und können folgende Monomeren enthalten:Suitable polyacrylates are OH group-containing polyacrylates with a hydroxyl number of 25 to 500. These should have an acid number <25, preferably <10 and a K value according to Fikentscher (3% in acetone) from 10 to 40, preferably from 12 to 25 and can contain the following monomers:

10 bis 100 Gew.%, vorzugsweise 20 bis 40 Gew.%, mindestens eines Hydroxy-(C2-C4)alkylesters einer α,β-ethylenisch ungesättigten Carbonsäure, beispielsweise 2-Hydroxyethyl- und Hydroxypropyl(meth-)acrylat sowie Butandiol-mono(meth-)acrylat, 0 bis 90 Gew.%, vorzugsweise 60 bis 80 Gew.%, mindestens einer ethylenisch umgesättigten von Carboxyl- und Hydroxylgruppen freien Verbindung, beispielsweise Vinylaromaten, wie Styrol und Vinyltoluol, Vinylester von Carbonsäuren mit 2 bis 18 Kohlenstoffatomen, wie Vinylacetat und Vinylpropionat, Vinylether von Monoalkanolen mit 1 bis 18 Kohlenstoffatomen, wie Vinylmethylether und Vinylisobutylether, Ester der Acrylsäure oder Methacrylsäure mit C₁- bis C₁₈-Monoalkanolen, entsprechende Maleinsäure-, Fumarsäure- und Itaconsäurediester, (Meth-) acrylsäureamid, (Meth-)acrylsäurenitril sowie Gemische dieser Monomeren, wobei Styrol und (Meth -) acrylsäureester bevorzugt sind.10 to 100% by weight, preferably 20 to 40% by weight, of at least one hydroxy (C2-C4) alkyl ester of an α, β-ethylenically unsaturated Carboxylic acid, for example 2-hydroxyethyl and hydroxypropyl (meth) acrylate and butanediol mono (meth) acrylate, 0 to 90% by weight, preferably 60 to 80% by weight, of at least one ethylenically unsaturated compound free of carboxyl and hydroxyl groups , for example vinyl aromatics, such as styrene and vinyl toluene, vinyl esters of carboxylic acids having 2 to 18 carbon atoms, such as vinyl acetate and vinyl propionate, vinyl ethers of monoalkanols having 1 to 18 carbon atoms, such as vinyl methyl ether and vinyl isobutyl ether, esters of acrylic acid or methacrylic acid with C₁ to C₁₈ monoalkanols, corresponding maleic acid, fumaric acid and itaconic acid diesters, (meth) acrylic acid amide, (meth) acrylonitrile and mixtures of these monomers, styrene and (meth) acrylic acid esters being preferred.

Geeignete Polyurethane sind:Suitable polyurethanes are:

OH-gruppenhaltige Polyurethane mit einer Hydroxylzahl von 25 bis 600 aus aliphatischen und/ oder aromatischen Diisocyanaten, die beispielsweise aus Tetramethylendiisocyanat, Hexamethylendiisocyanat, Isophorondiisocyanat, Diphenylmethandiisocyanat, Toluylendiisocyanat, Naphthylendiisocyanat, 4,4′-Diphenyletherdiisocyanat, sowie gegebenenfalls daraus hervorgehende Di- oder Trimere, und aliphatischen Diolen, wie Ethylenglykol, Diethylenglykol, Triethylenglykol, Polyethylenglykole, Propandiol, Butandiol, Hexandiol, Neopentylglykol oder Hydroxypivalinsäureneo-pentylglykolester und gegebenenfalls höherwertigen Alkoholen, wie Trimethylolpropan, Glycerin, Pentaerythrit, Trimethylolbenzol oder Trishydroxyethylisocyanurat erhältlich sind.OH-group-containing polyurethanes with a hydroxyl number of 25 to 600 from aliphatic and / or aromatic diisocyanates, which for example consist of tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, naphthylene diisocyanate, 4,4'-diphenyl ether or diisocyanate, and optionally diisocyanate, and aliphatic diols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, propanediol, butanediol, hexanediol, neopentyl glycol or hydroxypivalic acid neo-pentylglycol esters and optionally higher alcohols, such as trimethylolpropane, glycerol, pentaerythritol or tri-methyl-hydroxybenzurethyl, are available.

Geeignete Polyurethanharnstoffe sind entsprechende Umsetzungsprodukte aus den genannten Polyisocyanaten und den genannten aliphatischen Diolen bzw. höherwertiyen Alkoholen im Gemisch mit aliphatischen Diaminen, wie beispielsweise Ethylendiamin, Propylendiamin, 1,4-Butandiamin, 1,5-Pentandiamin, Neopentandiamin, Hexamethylendiamin, Diaminocyclohexan, Diaminodicyclohexylmethan, 3,3-Dimethyl-4,4′-diamin-dicyclohexylmethan, 4,9-Dioxadodecan-1,12-diamin, und gegebenenfalls höherwertigen Aminen, wie beispielsweise Trisaminoethyl-amin oder 1,1,1-Trisaminopropoxymethyl-propan.Suitable polyurethane ureas are corresponding reaction products of the polyisocyanates mentioned and the aliphatic diols mentioned or higher alcohols in a mixture with aliphatic diamines, such as, for example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, neopentanediamine, hexamethylenediamine, diaminocyclohexane, diaminodicyclohexane, diaminodiaminodicyclohexane, 3,3-dimethyl-4,4'-diamine-dicyclohexylmethane, 4,9-dioxadodecane-1,12-diamine, and optionally higher-value amines, such as trisaminoethyl-amine or 1,1,1-trisaminopropoxymethyl-propane.

Auch reine Polyharnstoffe, beispielsweise aus den genannten Polyisocyanaten und den genannten Polyaminen können als Komponente (A) in den erfindungsgemässen Überzugsmitteln eingesetzt werden.Pure polyureas, for example from the polyisocyanates mentioned and the polyamines mentioned, can also be used as component (A) in the coating compositions according to the invention.

Geeignete Epoxidharze sind z.B. Glycidylether, wie sie aus 2,2-Bis-(4-hydroxyphenyl)-propan und Epichlorhydrin hergestellt werden. Diese Epoxidharze können weiter modifiziert sein, z.B. durch Umsetzung mit polyfunktionellen Alkoholen oder SH-Verbindungen. Beispiele solcher polyfunktioneller Alkohole sind Ethylenglykol, Propandiol-1,2, Propandiol-1,3, Butandiol-1,4. Ist eine Elastifizierung erwünscht, können auch langkettige polyfunktionelle Alkohole oder Mercaptane eingesetzt werden. Werden die polyfunktionellen Alkohole oder Mercaptane in grösseren als äquivalenten Mengen in bezug auf die vorhandenen Epoxid-gruppen eingesetzt, so entstehen Produkte mit endständigen OH- oder SH-Gruppen. Setzt man dagegen geringere als äquivalente Mengen ein, so entstehen Produkte mit endständigen Epoxidgruppen, die gegebenenfalls weiter umgesetzt werden können. Während die Umsetzung der Mercaptane mit Epoxidgruppen bereits ohne Katalysator abläuft, sind für die Umsetzung der Alkohole die Verwendung eines Katalysators, wie z.B. Dimethylbenzylamin und höhere Temperaturen (etwa 50 bis 150°C) notwendig.Suitable epoxy resins are, for example, glycidyl ethers, such as those produced from 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin. These epoxy resins can be modified further, for example by reaction with polyfunctional alcohols or SH compounds. Examples of such polyfunctional alcohols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol. If elasticization is desired, long-chain polyfunctional alcohols or mercaptans can also be used. Are the polyfunctional alcohols or mercaptans in larger than equivalent Amounts used in relation to the epoxy groups present result in products with terminal OH or SH groups. If, on the other hand, less than equivalent amounts are used, products with terminal epoxy groups are formed, which can optionally be reacted further. While the reaction of the mercaptans with epoxy groups takes place without a catalyst, the use of a catalyst, such as dimethylbenzylamine and higher temperatures (about 50 to 150 ° C.) are necessary for the reaction of the alcohols.

Umsetzungsprodukte von Epoxidharzen mit primären oder sekundären Aminen sind ebenfalls als Komponente (A) einsetzbar. Dabei bietet sich besonders die Umsetzung mit hydroxylgruppenhaltigen Aminen, wie z.B. Ethanolamin, Methylethanolamin und Diethanolamin an.Reaction products of epoxy resins with primary or secondary amines can also be used as component (A). The reaction with hydroxyl-containing amines, such as e.g. Ethanolamine, methylethanolamine and diethanolamine.

Werden als Komponente (A) solche Produkte eingesetzt, die ausreichende Mengen an Amino-gruppen enthalten, um nach Protonierung mit Säuren wasserlöslich oder wasserdispergierbar zu werden, lassen sich in Kombination mit Komponente (B) wasserdispergierbare Einbrennlackbindemittel herstellen, insbesondere solche, die für die kathodische Elektrotauchlackierung verwendet werden können. Für diesen Zweck können die oben erwähnten Umsetzungsprodukte von Epoxidharzen mit primären oder sekundären Aminen eingesetzt werden.If such products are used as component (A) which contain sufficient amounts of amino groups in order to become water-soluble or water-dispersible after protonation with acids, water-dispersible stoving enamel binders can be prepared in combination with component (B), in particular those which are intended for the cathodic Electrocoating can be used. The above-mentioned reaction products of epoxy resins with primary or secondary amines can be used for this purpose.

Viele der für die kathodische Elektrotauchlackierung vorgeschlagenen Trägerharze sind auch als Komponente (A) in den erfindungsgemässen Überzugsmitteln einsetzbar, so z.B. die Umsetzungsprodukte phenolischer Mannichbasen mit Epoxidharzen gemäss der DE-PS 2419179, die Umsetzungsprodukte von kettenverlängerten Epoxidharzen mit sekundären Aminen gemäss der US-PS 4104147, Umsetzungsprodukte von (meth)acrylamidomethylierten Phenolen, Aminen und Epoxidharzen gemäss EP 27 641, EP 41 619 etc; wichtig ist nur, dass sie ein mittleres Molekulargewicht Mn von 500 bis 10000 aufweisen und im Mittel pro Molekül minöestens zwei OH- und/oder primäre und/oder sekundäre Amino-Gruppen besitzen. Während es für die Vernetzungsaktivität beim Einbrennen völlig ausreicht, wenn die Komponente (A) lediglich OH- und keine primäre und/ oder sekundäre Amino-Gruppen enthält, ist es doch häufig vorteilhaft, Produkte einzusetzen, die auch primäre und/oder sekundäre Amino-gruppen enthalten, da sich damit wässerige Elektrotauchlackbäder mit relativ hohen pH-Werten von z.B. 6,5 bis 8,0 herstellen lassen. Durch hohe pH-Werte, vor allem solche nahe pH 7 oder darüber, lässt sich eine Korrosion von Anlagen vermeiden.Many of the carrier resins proposed for cathodic electrocoating can also be used as component (A) in the coating compositions according to the invention, for example the reaction products of phenolic Mannich bases with epoxy resins according to DE-PS 2419179, the reaction products of chain-extended epoxy resins with secondary amines according to US-PS 4104147 , Reaction products of (meth) acrylamidomethylated phenols, amines and epoxy resins according to EP 27 641, EP 41 619 etc; it is only important that they have an average molecular weight M n of 500 to 10,000 and on average have at least two OH and / or primary and / or secondary amino groups per molecule. While it is entirely sufficient for the crosslinking activity when stoving if component (A) contains only OH groups and no primary and / or secondary amino groups, it is often advantageous to use products which also contain primary and / or secondary amino groups included, since it can be used to produce aqueous electro-dip lacquer baths with relatively high pH values of, for example, 6.5 to 8.0. High pH values, especially those close to pH 7 or above, prevent plant corrosion.

Eine Möglichkeit, um zu als Komponente (A) geeigneten Produkten mit primären und sekundären Aminogruppen zu kommen, ist die Umsetzung von überschüssigen primären Diaminen mit Epoxidharzen und anschliessende Abtrennung des überschüssigen Amins bei erhöhter Temperatur und vermindertem Druck. Als Diamine kommen dafür vor allem solche mit 2 bis 6 Kohlenstoffatomen in Betracht, z.B. Ethylendiamin, 1,2- und 1,3-Diaminopropan, 1,4-Diaminobutan, Neopentandiamin und Hexamethylendiamin. Die Reaktionsprodukte können, falls gewünscht, mit Dicarbonsäuren kettenverlängert werden, z.B. mit Sebacinsäure oder dimerer Fettsäure. Durch das Verhältnis Dicarbonsäure zu Epoxid/Amin-Addukt kann man das gewünschte Molekulargewicht einstellen, z. B. kann man auf zwei Moleküle Epoxid/Amin-Addukt 1 Mol dimerer Fettsäure einsetzen.One way of obtaining products with primary and secondary amino groups suitable as component (A) is to react excess primary diamines with epoxy resins and then separate the excess amine at elevated temperature and reduced pressure. Suitable diamines are, in particular, those having 2 to 6 carbon atoms, for example ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, neopentanediamine and hexamethylenediamine. If desired, the reaction products can be chain-extended with dicarboxylic acids, for example with sebacic acid or dimeric fatty acid. The ratio of dicarboxylic acid to epoxy / amine adduct allows the desired molecular weight to be set, e.g. B. you can use 1 mol of dimeric fatty acid on two molecules of epoxy / amine adduct.

Eine weitere Möglichkeit, als Komponente (A) geeignete Produkte mit primären Aminogruppen herzustellen, ist der Umsatz von Epoxidharzen mit sekundären Aminen, die geblockte primäre Aminogruppen enthalten. Beispiele für solche Amine sind das Diketimin von Diethylentriamin, das Ketimin von Aminoethylethanolamin, das Ketimin von Diethylentriamin, das Ketimin von Aminoethylethanolamin, das Ketimin von N-Methyl-ethylendiamin und das Ketimin von N-Aminoethylpiperazin. Die Ketimine lassen sich in einfacher Weise aus den freien Aminen und einem Keton, z.B. Methylisobutylketon, unter Auskreisen von Wasser herstellen. Bei der Umsetzung mit Epoxidharzen reagiert nur die sekundäre Aminogruppe, anschliessend kann das Ketimin durch einfache Zugabe von Wasser gespalten werden, wobei sich die freie primäre Aminogruppe zurückbildet.A further possibility of producing suitable products with primary amino groups as component (A) is the conversion of epoxy resins with secondary amines which contain blocked primary amino groups. Examples of such amines are the diketimine of diethylenetriamine, the ketimine of aminoethylethanolamine, the ketimine of diethylenetriamine, the ketimine of aminoethylethanolamine, the ketimine of N-methylethylenediamine and the ketimine of N-aminoethylpiperazine. The ketimines can be easily derived from the free amines and a ketone, e.g. Prepare methyl isobutyl ketone by removing water. When reacting with epoxy resins, only the secondary amino group reacts, then the ketimine can be split off by simply adding water, the free primary amino group regressing.

Durch Umsetzung eines Teils der primären Aminogruppen mit Dicarbonsäuren lassen sich auch diese Produkte durch Kettenverlängerung elastifizieren.By reacting some of the primary amino groups with dicarboxylic acids, these products can also be elasticized by chain extension.

Komponente (A) ist im erfindungsgemässen Bindemittelgemisch in einer Menge von 1 bis 90, vorzugsweise 50 bis 85 Gew.%, insbesondere 65 bis 80 Gew.% enthalten.Component (A) is contained in the binder mixture according to the invention in an amount of 1 to 90, preferably 50 to 85% by weight, in particular 65 to 80% by weight.

(B) Bei der Komponente (B) handelt es sich um ein Umsetzungsprodukt aus

  • a) mindestens einem Polyamin, das mindestens zwei primäre Aminogruppen pro Molekül und gegebenenfalls zusätzlich OH-Gruppen enthält, und
  • b) 75 bis 200 Mol.%, vorzugsweise 100 bis 150 Mol.%, bezogen auf die primären Aminogruppen der Komponente (a), mindestens eines cyclischen Kohlensäureesters der Formel (I)
Figure imgb0003
 worin R¹, R², R³ und R⁴ untereinander gleich oder verschieden sind und entweder für Wasserstoff, einen Methyl- oder einen Ethylrest stehen mit der Maßgabe, daß mindestens zwei Reste für Methyl und/oder Ethyl stehen.(B) Component (B) is a reaction product from
  • a) at least one polyamine which contains at least two primary amino groups per molecule and optionally additionally OH groups, and
  • b) 75 to 200 mol%, preferably 100 to 150 mol%, based on the primary amino groups of component (a), of at least one cyclic carbonic acid ester of the formula (I)
Figure imgb0003
 wherein R¹, R², R³ and R⁴ are the same or different from each other and are either hydrogen, a methyl or an ethyl radical, with the proviso that at least two radicals are methyl and / or ethyl.

Komponente (B) ist in den erfindungsgemässen Überzugsmitteln in Mengen von 10 bis 99 Gew.%, vorzugsweise 15 bis 50 Gew.%, insbesondere 20 bis 35 Gew.% enthalten.Component (B) is present in the coating compositions according to the invention in amounts of 10 to 99% by weight, preferably 15 to 50% by weight, in particular 20 to 35% by weight.

Als Polyamin (a) kommen prinzipiell alle aliphatischen und araliphatischen Polyamine in Frage, die mindestens zwei primäre Aminogruppen pro Molekül enthalten. Beispiele geeigneter Amine sind Ethylendiamin, Propylendiamin, 1,4-Diaminobutan, 1,5-Diaminopentan, Neopentandiamin, Hexamethylendiamin, 4,9-Dioxadodecandiamin-1,12, 4,4′-Diaminodicyclohexylamin, 4,4′-Bis (amino-ethoxy)-2,2-diphenylpropan, 4,4′-Bis (aminopropoxy)-2,2-diphenylpropan, Tris-(aminoethyl)-amin, 1,1,1-Tris-aminopropoxymethylpropan, β,β-Bis-(aminomethyl)-n-butylamin, Tetrakis-(aminomethyl)-methan, Tris-(aminoethyl)-isocyanurat und Tris-(aminomethyl)benzol, wobei in den letztgenannten sechs Beispielen ein Teil der Aminogruppen durch OH-Gruppen ersetzt sein kann, derart, dass im Mittel mindestens zwei primäre Aminogruppen pro Molekül enthalten sind.In principle, all aliphatic and araliphatic polyamines which contain at least two primary amino groups per molecule are suitable as polyamine (a). Examples of suitable amines are ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane, neopentanediamine, Hexamethylene diamine, 4,9-dioxadodecane diamine-1,12, 4,4'-diaminodicyclohexylamine, 4,4'-bis (amino-ethoxy) -2,2-diphenylpropane, 4,4'-bis (aminopropoxy) -2.2 -diphenylpropane, tris (aminoethyl) amine, 1,1,1-tris-aminopropoxymethylpropane, β, β-bis (aminomethyl) -n-butylamine, tetrakis (aminomethyl) methane, tris (aminoethyl) isocyanurate and tris (aminomethyl) benzene, in the latter six examples a part of the amino groups can be replaced by OH groups, such that on average at least two primary amino groups are contained per molecule.

Als weitere Beispiele für geeignete Polyamine (a) sind Amidamine zu nennen, die beispielsweise durch Umsetzung von Polycarbonsäuren, wie z.B. Phthalsäure, Isophthalsäure, Terephthalsäure, Trimellitsäure, Trimesinsäure, Pyromellitsäure und dgl. bzw. deren Anhydriden mit Überschüssen an Diaminen, wie beispielsweise Propylendiamin, 1,4-Diaminobutan, 1,5-Diaminopentan, Neopentandiamin, Hexamethylendiamin und dgl. bei erhöhten Temperaturen unter Wasserabspaltung nach destillativer Entfernung des überschüssigen Diamins im Vakuum erhalten werden.Further examples of suitable polyamines (a) include amidamines which are obtained, for example, by reacting polycarboxylic acids, e.g. Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid and the like, or their anhydrides with excess diamines, such as, for example, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane, neopentanediamine, hexamethylenediamine and the like at elevated temperatures under water cleavage after removing the excess diamine by distillation in vacuo.

Neben derartigen Polyaminen mit niedrigem, definiertem Molekulargewicht sind auch oligomere oder polymere Polyamine mit Molekulargewichten bis zu 3000 einsetzbar. Beispiele solcher Polyamine sind Diamine, die durch reduktive Cyanethylierung von Polyolen wie Polytetrahydrofuran herstellbar sind. Derartige Produkte enthalten endständige primäre Aminogruppen in Form von Aminopropoxygruppen. Sie können noch mehr oder weniger grosse Mengen an OH-Gruppen enthalten.In addition to such polyamines with a low, defined molecular weight, oligomeric or polymeric polyamines with molecular weights up to 3000 can also be used. Examples of such polyamines are diamines which can be prepared by reductive cyanoethylation of polyols such as polytetrahydrofuran. Such products contain terminal primary amino groups in the form of aminopropoxy groups. They can still contain more or less large amounts of OH groups.

Bei einer weiteren Gruppe von oligomeren oder polymeren Polyaminen mit Molekulargewichten bis zu 3000, die als Komponente (a) geeignet sind, handelt es sich um Epoxid/Amin-Addukte, die im Mittel mindestens zwei primäre Aminogruppen pro Molekül und ausserdem OH-Gruppen enthalten. Ihre Herstellung kann im wesentlichen auf zwei Wegen erfolgen.Another group of oligomeric or polymeric polyamines with molecular weights up to 3000, which are suitable as component (a), are epoxy / amine adducts which contain on average at least two primary amino groups per molecule and also OH groups. They can be manufactured essentially in two ways.

Der erste besteht in der Umsetzung von Epoxidharzen mit überschüssigen primären Diaminen und der anschliessenden Abtrennung des überschüssigen Diamins bei erhöhter Temperatur und vermindertem Druck.The first consists in the reaction of epoxy resins with excess primary diamines and the subsequent separation of the excess diamine at elevated temperature and reduced pressure.

Dafür geeignete Epoxidharze sind z.B. Polyglycidylether von Polyphenolen, wie beispielsweise 2,2-Bis-(4-hydroxyphenyl)-propan, 1,1-Bis-(4-hydroxyphenyl)-ethan, Bis-(4-hydroxyphenyl)-methan, Bis-(2-hydroxynaphthyl)-methan und dgl., die durch Veretherung der genannten Polyphenole mit Epichlorhydrin in Gegenwart von Alkali hergestellt werden, Polyglycidylether von mehrwertigen Alkoholen, die durch entsprechende Umsetzung von Epichlorhydrin mit mehrwertigen Alkoholen, wie Ethylenglykol, Diethylenglykol, Triethylenglykol, Propandiol-1,2, Propandiol-1,3, Pentandiol-1,5, 2,2-Bis-(4-hydroxycyclohexyl)-propan, Glycerin, Trimethylolpropan, Pentaerythrit und dgl. erhalten werden, N,N-Diglycidyl-Derivate von N-Heterocyclen und Triglycidylisocyanurat.Suitable epoxy resins are, for example, polyglycidyl ethers of polyphenols, such as, for example, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, bis - (2-hydroxynaphthyl) methane and the like, which are prepared by etherification of the polyphenols mentioned with epichlorohydrin in the presence of alkali, polyglycidyl ethers of polyhydric alcohols, which are reacted by appropriate reaction of epichlorohydrin with polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, propanediol -1,2, propanediol-1,3, pentanediol-1,5, 2,2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethylolpropane, pentaerythritol and the like can be obtained, N, N-diglycidyl derivatives of N-heterocycles and triglycidyl isocyanurate.

Aus Elastizitätsgründen kann es von Vorteil sein, die genannten Epoxidharze vor der Umsetzung mit Aminen mit geringeren als äquivalenten Mengen an langkettigen polyfunktionellen Alkoholen oder Mercaptanen zu modifizieren.For reasons of elasticity, it may be advantageous to modify the epoxy resins mentioned with smaller than equivalent amounts of long-chain polyfunctional alcohols or mercaptans before the reaction with amines.

Auch eine Elastifizierung durch langkettige Disek.-Amine, wie beispielsweise Dimerfettsäure-bis-[2-(2-hydroxyethylamino)-ethyl]-amid, die ebenfalls in geringeren als äquivalenten Mengen eingesetzt werden, ist möglich. In diesem Falle können Elastifizierung und Aminumsetzung synchron durchgeführt werden.Elasticization by means of long-chain dis-amines, such as, for example, dimer fatty acid bis- [2- (2-hydroxyethylamino) ethyl] amide, which are also used in smaller than equivalent amounts, is possible. In this case, elastification and amine conversion can be carried out synchronously.

Als Diamine kommen hierfür vor allem solche mit 2 bis 6 Kohlenstoffatomen in Betracht, z.B. Ethylendiamin, 1,2- und 1,3-Diaminopropan, 1,4-Diaminobutan, Neopentandiamin und Hexamethylendiamin. Die Reaktionsprodukte können, falls keine vorherige Elastifizierung erfolgt ist, mit Dicarbonsäuren kettenverlängert werden, z.B. mit Sebacinsäure oder dimerer Fettsäure. Durch das Verhältnis Dicarbonsäure zu Epoxid/Amin-Addukt kann man das gewünschte Mölekulargewicht einstellen, z.B. kann man auf zwei Moleküle Epoxid/Amin-Addukt 1 Mol dimerer Fettsäure einsetzen.Suitable diamines for this purpose are especially those with 2 to 6 carbon atoms, e.g. Ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, neopentanediamine and hexamethylenediamine. The reaction products can, if no previous elasticization has taken place, be chain-extended with dicarboxylic acids, e.g. with sebacic acid or dimeric fatty acid. The ratio of dicarboxylic acid to epoxy / amine adduct can be used to set the desired molecular weight, e.g. one can use 1 mol of dimeric fatty acid on two molecules of epoxy / amine adduct.

Der zweite Weg besteht in der Umsetzung der genannten Epoxidharze mit sekundären Aminen, die geblockte primäre Aminogruppen enthalten. Beispiele für solche Amine sind das Diketimin von Diethylentriamin, das Ketimin von Aminoethyl-ethanolamin, das Ketimin von N-Aminoethyl-piperazin und das Ketimin von N-Methyl-ethylendiamin. Die Ketimine lassen sich in einfacher Weise aus den freien Aminen und einem Keton, z.B. Methylisobutylketon, unter Auskreisen von Wasser herstellen. Bei der Umsetzung mit Epoxidharzen reagiert nur die sekundäre Aminogruppe; anschliessend kann das Ketimin durch einfache Zugabe von Wasser gespalten werden, wobei sich die freie primäre Aminogruppe zurückbildet. Durch Umsetzung eines Teils der primären Aminogruppen mit Dicarbonsäuren lassen sich auch diese Produkte durch Kettenverlängerung elastifizieren.The second way consists in the reaction of the epoxy resins mentioned with secondary amines which contain blocked primary amino groups. Examples of such amines are the diketimine of diethylenetriamine, the ketimine of aminoethylethanolamine, the ketimine of N-aminoethylpiperazine and the ketimine of N-methylethylenediamine. The ketimines can be easily derived from the free amines and a ketone, e.g. Prepare methyl isobutyl ketone by removing water. When reacting with epoxy resins, only the secondary amino group reacts; the ketimine can then be cleaved by simply adding water, the free primary amino group regressing. By reacting some of the primary amino groups with dicarboxylic acids, these products can also be elasticized by chain extension.

Als Komponente (b) geeignete cyclische Kohlensäureester sind beispielsweise Isobutylencarbonat, Butylen-2,3-carbonat. Sie sind in einfacher Weise aus den entsprechenden Epoxiden durch Umsetzung mit Kohlendioxid erhältlich.Cyclic carbonic acid esters suitable as component (b) are, for example, isobutylene carbonate, butylene-2,3-carbonate. They can be obtained in a simple manner from the corresponding epoxides by reaction with carbon dioxide.

Die Umsetzung der Komponente (a) mit der Komponente (b) erfolgt entweder in Substanz oder in geeigneten Lösemitteln, wie beispielsweise Wasser, Alkoholen, Ethern, Estern, Ketonen, Halogenkohlenwasserstoffen, aromatischen Kohlenwasserstoffen und aliphatischen Kohlenwasserstoffen. Die Reaktionspartner sollen in den verwendeten Lösemitteln oder Lösemittelgemischen zumindest grösstenteils löslich sein und letztere seibst sollen weder primäre oder sekundäre Aminogruppen noch Mercaptogruppen enthalten, weiche auch mit den cyclischen Kohlensäureestern reagieren können. Die bevorzugten Lösemittel sind Wasser, Alkohole und Etheralkohole, wie beispielsweise Methanol, Ethanol, Propanole, Butanole und Monoether von Diolen, z.B. Ethylenglykol, Diethylenglykol, Propylenglykol oder Dipropylenglykol mit den zuerst genannten Monoalkanolen.The reaction of component (a) with component (b) takes place either in bulk or in suitable solvents, such as water, alcohols, ethers, esters, ketones, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons. The reactants should be at least largely soluble in the solvents or solvent mixtures used, and the latter themselves should not contain primary or secondary amino groups or mercapto groups, which can also react with the cyclic carbonic acid esters. The preferred solvents are water, alcohols and ether alcohols, such as methanol, ethanol, propanols, butanols and monoethers of diols, for example ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol with the monoalkanols mentioned first.

Die Umsetzung der Komponenten (a) und (b) erfolgt im allgemeinen bei Temperaturen von 0 bis 80°C, vorzugsweise 15 bis 40°C. In einer besonders bevorzugten Ausführungsform der Erfinduug werden die Reaktionspartner bei Raumtemperatur gemischt und stehengelassen, bis die erforderliche Aminzahlabnahme erfolgt ist. Die Reaktionszeiten liegen im Bereich zwischen etwa 1 und etwa 48 Stunden.Components (a) and (b) are generally reacted at temperatures from 0 to 80 ° C., preferably 15 to 40 ° C. In a particularly preferred embodiment of the invention, the reactants are mixed at room temperature and left to stand until the required amine number decrease has taken place. Response times range from about 1 to about 48 hours.

Zur Herstellung der erfindungsgemässen Überzugsmittel werden die Komponenten (A) und (B) gemischt. Bei Komponenten mit niedriger Viskosität kann dies in Substanz erfolgen, wobei gegebenenfalls auf Temperaturen bis maximal 130°C erwärmt wird. Produkte höherer Viskosität werden vor der Mischung in organischen Lösemitteln gelöst. Dabei können übliche Lösemittel wie Alkohole, Ketone, Ester, Ether, Kohlenwasserstoffe etc. verwendet werden.Components (A) and (B) are mixed to produce the coating compositions according to the invention. In the case of components with low viscosity, this can take place in bulk, where appropriate heating to temperatures of up to 130 ° C. Products with higher viscosity are dissolved in organic solvents before mixing. Common solvents such as alcohols, ketones, esters, ethers, hydrocarbons etc. can be used.

Die erfindungsgemässen Überzugsmittel können zusammen mit löslichen Farbstoffen, Füllstoffen, Pigmenten oder dgl. nach üblichen Methoden zu organisch gelösten Lacken verarbeitet werden. Diese können zusätzlich in der Lacktechnologie übliche Zusatzstoffe, wie Verlaufshilfsmittel, Entschäumer, Netzmittel, Härtungskatalysatoren sowie in untergeordneten Mengen zusätzliche Vernetzer und weitere Bindemittel enthalten.The coating compositions according to the invention can be processed together with soluble dyes, fillers, pigments or the like to form organically dissolved paints by customary methods. These can additionally contain additives customary in coating technology, such as leveling agents, defoamers, wetting agents, curing catalysts and, in minor amounts, additional crosslinking agents and other binders.

Ihre Verarbeitung kann nach üblichen Methoden erfolgen, wie durch Streichen, Rakeln, Spritzen, Walzen, Giessen oder Drucken. Bevorzugt ist die Verarbeitung durch Lackspritzen nach den verschiedenen Ausführungsformen, sei es mit Luftdruckspritzpistolen oder auf einer Elektrostatikanlage.They can be processed using customary methods, such as brushing, knife coating, spraying, rolling, casting or printing. Preference is given to processing by spraying paint in accordance with the various embodiments, be it with air pressure spray guns or on an electrostatic system.

Die Einbrenntemperaturen liegen im allgemeinen zwischen 130 und 200°C, vorzugsweise zwischen 150 und 180°C, die Einbrennzeiten bei 20 bis 30 Minuten, sofern mit Härtungskatalysatoren gearbeitet wird.The stoving temperatures are generally between 130 and 200 ° C, preferably between 150 and 180 ° C, the stoving times are 20 to 30 minutes, provided that curing catalysts are used.

Als Härtungskatalysatoren sind Zinnverbindungen, wie beispielsweise Dibutylzinndilaurat, Dibutylzinnoxid, Zinnacetat und dgl., bevorzugt. Geeignet sind auch Bleiverbindungen, wie beispielsweise Bleinaphthenat, Bleioctoat oder Bleiacetat. Die Zusätze erfolgen in Mengen von 0,5 bis 4 Gew.%, vorzugsweise 1 bis 2,5 Gew.%, bezogen auf das Lackbindemittel.Tin compounds such as dibutyltin dilaurate, dibutyltin oxide, tin acetate and the like are preferred as hardening catalysts. Lead compounds such as lead naphthenate, lead octoate or lead acetate are also suitable. The additions are made in amounts of 0.5 to 4% by weight, preferably 1 to 2.5% by weight, based on the paint binder.

Für die Herstellung von Pulverlacken werden jeweils feste Komponenten (A) und (B), deren Erweichungsprodukte aus Gründen der Blockfestigkeit jeweils > 60°C liegen sollten, trocken gemahlen und mit üblichen Zusätzen, wie Pigmenten, Füllstoffen und in untergeordneten Mengen Härtungskatalysatoren und Verlaufshilfsmitteln, beispielsweise auf Polyacrylatbasis, vermischt. Die Mischungen werden anschliessend bei Temperaturen um 100°C schmelzhomogenisiert (z.B. im Extruder). Nach Abkühlen der Extrudate auf Raumtemperatur werden diese gründlich gemahlen und die unterhalb einer Teilchengrösse von ca. 90 µm liegenden Pulverlackanteile durch Sieben abgetrennt. Die darüber liegenden Anteile werden bei weiteren Mahlungen erneut eingesetzt.For the production of powder coatings, solid components (A) and (B), the softening products of which should be> 60 ° C for reasons of blocking resistance, are ground dry and with conventional additives such as pigments, fillers and in minor amounts hardening catalysts and leveling agents, for example based on polyacrylate. The mixtures are then melt-homogenized at temperatures around 100 ° C (eg in an extruder). After cooling the extrudates These are thoroughly ground at room temperature and the powder coating components below a particle size of approx. 90 µm are separated off by sieving. The parts above are used again for further grinding.

Die Applikation der Pulverlacke erfolgt in üblicher Weise durch elektrostatisches Pulversprühen. Die Einbrennbedingungen stimmen mit denen der konventionellen Lacke überein.The powder coatings are applied in the customary manner by electrostatic powder spraying. The stoving conditions are the same as for conventional paints.

Werden die oben beschriebenen Pulverlacke einer nachträglichen Nassmahlung in Wasser unterzogen, bis eine Partikelgrösse < 10 bis 20 µm erreicht ist, erhält man stabile wässerige Pulversuspensionen, die wie die oben beschriebenen konventionellen Lacke appliziert und eingebrannt werden können. Bevorzugt ist auch hier die Verarbeitung durch Lackspritzen nach den verschiedenen Ausführungsformen, sei es mit Luftdruckspritzpistolen oder auf einer Elektrostatikanlage.If the powder coatings described above are subjected to a subsequent wet grinding in water until a particle size of <10 to 20 µm is obtained, stable aqueous powder suspensions are obtained which can be applied and baked like the conventional coatings described above. Here too, preference is given to processing by paint spraying according to the various embodiments, be it with air pressure spray guns or on an electrostatic system.

Werden in den erfindungsgemässen Überzugsmitteln als Komponente (A) Epoxid/Amin-Addukte eingesetzt, so sind diese nach Protonierung mit Säuren wasserlöslich oder dispergierbar. Sie lassen sich somit als Bindemittel für kathodisch abscheidbare Elektrotauchlacke einsetzen.If epoxy / amine adducts are used as component (A) in the coating compositions according to the invention, they are water-soluble or dispersible after protonation with acids. They can therefore be used as binders for cathodically depositable electrocoat materials.

Die Herstellung der Elektrotauchlacke erfolgt nach üblichen Methoden. Als Neutralisationsmittel werden anorganische und organische Säuren, wie Ameisensäure, Essigsäure, Milchsäure oder Phosphorsäure, verwendet, wobei Carbonsäuren bevorzugt sind. Ihre Mengen sind so bemessen, dass Bad-p-Werte von 6,5 bis 8,0, vorzugsweise 7,0 bis 7,5, resultieren, damit eine Korrosion der Anlagen vermieden wird. Die Bäder können ausserdem weitere übliche Zusatzstoffe, wie Pigmente, Füllstoffe, Verlaufmittel, Netzmittel, oberflächenaktive Mittel sowie in untergeordneten Mengen zusätzliche andere Lackbindemittel und/oder Vernetzer enthalten.Electrodeposition paints are produced by customary methods. Inorganic and organic acids such as formic acid, acetic acid, lactic acid or phosphoric acid are used as neutralizing agents, carboxylic acids being preferred. Their quantities are such that Bad p values of 6.5 to 8.0, preferably 7.0 to 7.5, result, so that corrosion of the systems is avoided. The baths can also contain other customary additives, such as pigments, fillers, leveling agents, wetting agents, surface-active agents and, in minor amounts, additional other paint binders and / or crosslinking agents.

Auch bei dieser Anwendung der erfindungsgemässen Lackbindemittel ist in der Regel der Einsatz von Härtungskatalysatoren von Vorteil, deren Art und Menge bereits oben bei der Verwendung in konventionellen Lacken beschrieben wurden.In this application of the paint binders according to the invention, too, it is generally advantageous to use curing catalysts, the type and amount of which have already been described above for use in conventional paints.

Die erfindungsgemässen Überzugsmittel lassen sich so für das Überziehen von beliebigen elektrisch leitenden Substraten, wie beispielsweise Eisen, das gegebenenfalls chemisch vorbehandelt, z.B. phosphatiert sein kann, Aluminium, Kupfer und dgl., verwenden.The coating compositions according to the invention can thus be used for coating any electrically conductive substrates, such as iron, which may have been chemically pretreated, e.g. can be phosphated, use aluminum, copper and the like.

Die Abscheidespannungen betragen im allgemeinen 50 bis 500 V, vorzugsweise 150 bis 350 V. Für die Härtung der abgeschiedenen Überzüge sind Einbrennbedingungen erforderlich, wie sie bereits bei der Beschreibung der konventionellen Systeme beschrieben wurden.The deposition voltages are generally 50 to 500 V, preferably 150 to 350 V. For the hardening of the deposited coatings, baking conditions are required, as have already been described in the description of the conventional systems.

Die folgenden Beispiele sollen die vorliegende Erfindung näher erläutern, ohne diese einzuschränken. Die in den Beispielen angegebenen Teile und Prozente beziehen sich, soweit nicht anders angegeben, auf das Gewicht.The following examples are intended to illustrate the present invention without restricting it. Unless stated otherwise, the parts and percentages given in the examples relate to the weight.

Beispiel 1:Example 1:

Beispiel 1 beschreibt die Herstellung eines organisch gelösten Einbrennlacks, der als Komponente (A) ein Polyacrylatharz enthält.Example 1 describes the preparation of an organic dissolved stoving lacquer, which contains a polyacrylate resin as component (A).

a) Herstellung des Polyacrylatharzesa) Production of the polyacrylate resin

In einern Kolben mit Rührer, Rückflusskühler und Innenthermometer werden 800 Teile Essigsäure-n-butylester vorgelegt und unter Rühren in einer Stickstoffatmosphäre auf 100°C erwärmt. Anschliessend werden bei 100°C der Zulauf I, bestehend aus 520 Teilen Butandiolmonoacrylat, 610 Teilen tert.-Butylacrylat, 660 Teilen n-Butylacrylat, 200 Teilen Methylmethacrylat und 10 Teilen Acrylsäure, binnen 4 Stunden und der Zulauf II, bestehend aus 540 Teilen Essigsäure-n-butylester und 50 Teilen Azo-bis- isobutyronitril, binnen 6 Stunden zugetropft. Die entstehende 60%ige Lösung des Polyacrylatharzes in Essigsäure-n-butylester weist einen K-Wert nach Fikentscher von 24 (3%ig in Dimethylformamid), eine Säurezahl von 1 mg KOH/g und eine OH-Zahl von 98 mg KOH/g auf.800 parts of n-butyl acetate are placed in a flask equipped with a stirrer, reflux condenser and internal thermometer and heated to 100 ° C. with stirring in a nitrogen atmosphere. Subsequently, at 100 ° C., feed I, consisting of 520 parts of butanediol monoacrylate, 610 parts of tert-butyl acrylate, 660 parts of n-butyl acrylate, 200 parts of methyl methacrylate and 10 parts of acrylic acid, are added within 4 hours, and feed II, consisting of 540 parts of acetic acid -n-butyl ester and 50 parts of azo-bis-isobutyronitrile, added dropwise within 6 hours. The resulting 60% solution of the polyacrylate resin in n-butyl acetate has a Fikentscher K value of 24 (3% in dimethylformamide), an acid number of 1 mg KOH / g and an OH number of 98 mg KOH / g on.

b) Umsetzungsprodukt aus Tris-aminoethylamin und Isobutylencarbonatb) reaction product of tris-aminoethylamine and isobutylene carbonate

Zu einer 50%igen Lösung von 1000 Teilen Tris-aminoethyl-aimin in Ethanol wird bei Raumtemperatur unter Rühren eine 50%ige Lösung von 2522 Teilen Isobutylencarbonat in Ethanol hinzugefügt. Nach Abklingen der exothermen Reaktion (bis 40°C) lässt man die Mischung 48 Stunden bei Raumtemperatur stehen.A 50% solution of 2522 parts of isobutylene carbonate in ethanol is added to a 50% solution of 1000 parts of tris-aminoethylamine in ethanol at room temperature with stirring. After the exothermic reaction has subsided (up to 40 ° C.), the mixture is left to stand at room temperature for 48 hours.

c) Herstellung des organisch gelösten Einbrennlacksc) Production of the organically dissolved stoving lacquer

In einer Mischung aus 1000 Teilen des Acrylatharzes auf Beispiel 1a), 514 Teilen des Umsetzungsproduktes nach Beispiel 1b), 17 Teilen Dibutylzinndilaurat und 329 Teilen Ethylenglykolmonoethylether wird eine Mischung aus 214 Teilen Eisenoxidgelb, 107 Teilen 1.9-Anthrapyrimidin- 2-carbonsäure- anthrachinolylamid und 107 Teilen Titandioxid angeteigt und in einer Rührwerksrnühle mit 2100 Teilen Glasperlen (Durchmesser 2 mm) vermahlen, bis eine Körnigkeit nach DIN 53 203 von < 10 µm erreicht ist. Nach Abtrennen der Mahlkörper entsteht ein 55%iger Gelblack.A mixture of 214 parts of iron oxide yellow, 107 parts of 1,9-anthrapyrimidine-2-carboxylic acid anthraquinolylamide and 107 is obtained in a mixture of 1000 parts of the acrylate resin in Example 1a), 514 parts of the reaction product according to Example 1b), 17 parts of dibutyltin dilaurate and 329 parts of ethylene glycol monoethyl ether Parts of titanium dioxide are pasted and ground in a stirrer mill with 2100 parts of glass beads (diameter 2 mm) until a granularity according to DIN 53 203 of <10 µm is reached. After removing the grinding media, a 55% yellow varnish is created.

Dieser Lack wird mit wenig Essigsäure-n-butylester auf eine Auslaufzeit im DIN 4-Becher von 30 sec. verdünnt, auf Stahlbleche gespritzt und nach 5 minütigem Ablüften bei Rauinntemperatur 20 Minuten bei 160°C eingebrannt. Die eingebrannten Filme zeigen nach 50 maligem Hin- und Herreiben mit einem mit Methylisobutylketon getränkten Wattebausch keinen Angriff.This lacquer is diluted with a little n-butyl acetate to a run-out time of 30 seconds in a DIN 4 beaker, sprayed onto steel sheets and, after flashing off for 5 minutes at room temperature, baked at 160 ° C. for 20 minutes. After being rubbed back and forth 50 times with a cotton ball soaked in methyl isobutyl ketone, the baked films show no attack.

Schichtdicke: 30 µmLayer thickness: 30 µm

Glanz ≮ 60°: 83%Gloss ≮ 60 °: 83%

Pendelhärte nach König: 120 sec.Pendulum hardness according to König: 120 sec.

Erichsen Tiefung: 10 µmErichsen cupping: 10 µm

Beispiel 2:Example 2:

Beispiel 2 beschreibt die Herstellung eines organisch gelösten Einbrennlacks, der als Komponente (A) einen Polyester, speziell, ein Alkydharz enthält.Example 2 describes the preparation of an organically dissolved stoving lacquer which contains a polyester, especially an alkyd resin, as component (A).

a) Herstellung des Alkydharzesa) Preparation of the alkyd resin

In einem Kolben mit Rührer, Wasserabscheider und Innenthermometer wird eine Mischung aus 1100 Teilen Ricinenfettsäure, 666 Teilen Phthalsäureanhydrid, 828 Teilen Trimethylolpropan, 1 Teil hypophosphoriger Säure und 62 Teilen einer aromatischen Benzinfraktion (Siedebereich: 185 bis 206°C) unter Stickstoff auf 200 bis 220°C erhitzt und kondensiert bis eine Säurezahl von ca. 20 mg KOH/g erreicht ist. Nach dem Abkühlen wird der Rückstand mit 880 Teilen lsobutanol aufgenommen.In a flask equipped with a stirrer, water separator and internal thermometer, a mixture of 1100 parts of ricin fatty acid, 666 parts of phthalic anhydride, 828 parts of trimethylolpropane, 1 part of hypophosphorous acid and 62 parts of an aromatic gasoline fraction (boiling range: 185 to 206 ° C) under nitrogen to 200 to 220 ° C heated and condensed until an acid number of about 20 mg KOH / g is reached. After cooling, the residue is taken up in 880 parts of isobutanol.

Festkörpergehalt: 75%Solids content: 75%

OH-Zahl: 149 mg KOH/GOH number: 149 mg KOH / G

b) Herstellung des organisch gelösten Einbrennlacksb) Production of the organically dissolved stoving lacquer

In einer Mischung aus 1000 Teilen des Alkydharzes aus Beispiel 2a), 272 Teilen Xylol, 1500 Teilen dis Umsetzungsproduktes nach Beispiel 1b), 30 Teilen Dibutylzinndilaurat und 250 Teilen Ethylenglykolmonoethylether wird eine Mischung aus 375 Teilen Eisenoxidgelb, 187,5 Teilen 1.9-Anthrapyrimidin-2-carbonsäure-anthrachinolylamid und 187,5 Teilen Titandioxid angeteigt und in einer Rührwerksmühle mit 3300 Teilen Glasperlen (Durchmesser: 2 mm) vermahlen, bis eine Körnigkeit nach DIN 53 203 von < 10 µm erreicht ist. Nach Abtrennen der Mahlkörper entsteht ein 60%iger Gelblack.In a mixture of 1000 parts of the alkyd resin from Example 2a), 272 parts of xylene, 1500 parts of the reaction product according to Example 1b), 30 parts of dibutyltin dilaurate and 250 parts of ethylene glycol monoethyl ether, a mixture of 375 parts of iron oxide yellow, 187.5 parts of 1,9-anthrapyrimidine-2 -carboxylic acid-anthraquinolylamide and 187.5 parts of titanium dioxide pasted and ground in a stirrer mill with 3300 parts of glass beads (diameter: 2 mm) until a granularity according to DIN 53 203 of <10 µm is achieved. After removing the grinding media, a 60% yellow varnish is created.

Der Lack wird mit wenig Xylol auf eine Auslaufzeit in DIN 4-Becher von 30 sec verdünnt, auf Stahlbleche gesprizt und nach 5 minütigem Ablüften bei Raumtemperatur 20 Minuten bei 180°C eingebrannt. Die eingebrannten Filme zeigen nach 50 maligem Hin- und Herreiben mit einem mit Methylisobutylketon getränkten Wattbausch keinen Angriff.The lacquer is diluted with a little xylene to a run-out time in DIN 4 cups of 30 seconds, sprayed onto steel sheets and, after flashing off for 5 minutes at room temperature, baked at 180 ° C. for 20 minutes. The burned-in films show no attack after rubbing back and forth 50 times with a cotton ball soaked in methyl isobutyl ketone.

Schichtdicke: 25 µmLayer thickness: 25 µm

Glanz ≮ 60°: 85%Gloss ≮ 60 °: 85%

Pendelhärte nach König: 164 sec.Pendulum hardness according to König: 164 sec.

Erichsen Tiefung: 6,2 mmErichsen cupping: 6.2 mm

Beispiel 3:Example 3:

Beispiel 3 beschreibt die Herstellug eines organisch gelösten Einbrennlacks, der als Komponente (A) ein Epoxid/Amin-Addukt enthält, und beispielsweise als Füller für die Automobillackierung geeignet ist.Example 3 describes the production of an organically dissolved stoving lacquer which contains an epoxy / amine adduct as component (A) and is suitable, for example, as a filler for automotive coating.

a) Herstellung eines elastifizierten Epoxidharzesa) Production of an elasticized epoxy resin

1455 Teile eines handelsüblichen Pölyglycidylethers von 2.2-Bis-(4-hydroxyphenyl)-propan mit einem Epoxidäquivalentgewicht von 485 werden mit 412,5 Teilen eines handelsüblichen Polycaprolactondiols mit einem OH-Äquivalentgewicht von 275 in Gegenwart von 120 Teilen Xylol une 4,5 Teilen Dimethylbenzylamin ca. 2 Stunden bei 130°C umgesetzt. Das Epoxidäquivalentgewicht beträgt dann 1070. Das Harz wird mit 504 Teilen Isobutanol auf 75% Festkörper verdünnt und sofort, wie unter 3c) beschrieben, weiterverarbeitet.1455 parts of a commercially available polyglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane with an epoxy equivalent weight of 485 are mixed with 412.5 parts of a commercial polycaprolactone diol with an OH equivalent weight of 275 in the presence of 120 parts of xylene and 4.5 parts of dimethylbenzylamine implemented at 130 ° C for about 2 hours. The epoxy equivalent weight is then 1070. The resin is diluted to 50% solids with 504 parts of isobutanol and processed immediately, as described under 3c).

b) Herstellung eines Ketimins aus Methylisobutylketon und N-Aminoethyl-piperazinb) Preparation of a ketimine from methyl isobutyl ketone and N-aminoethyl-piperazine

387 Teile N-Aminoethyl-piperazin und 511 Teile Methylisobutylketon werden gemeinsam erhitzt. In einem Temperaturbereich von 113 bis 147°C werden binnen 3½ Stunden 54 Teile Wasser ausgekreist. Auf diese Weise wird eine ca. 75%ige Lösung des gewünschten Ketimins in Methylisobutylketon erhalten.387 parts of N-aminoethyl-piperazine and 511 parts of methyl isobutyl ketone are heated together. 54 parts of water are removed within 3½ hours in a temperature range from 113 to 147 ° C. In this way, an approximately 75% solution of the desired ketimine in methyl isobutyl ketone is obtained.

c) Herstellung des Epixod/Amin-Adduktesc) Preparation of the epixod / amine adduct

Zu 2480 Teilen des elastifizierten Epoxidharzes nach Beispiel 3a) (75%ige Lösung) werden 489 Teile Ketimin aus Beispiel 3b) (75%ige Lösung) gegeben und die Mischung 2 Stunden auf 100°C erwärmt. Der Epoxidwert ist dann auf 0 gefallen. Anschliessend werden zwecks Hydrolyse des Ketimins bei 120°C 100 Teile Wasser hinzugefügt. Die Mischung wird, gegebenenfalls unter Zugabe weiteren Wassers, so lange destilliert, bis kein Methylisobutylketon mehr übergeht. Der Rückstand wird dann mit Isobutanol auf einen Festkörpergehalt von 65% verdünnt.489 parts of ketimine from Example 3b) (75% solution) are added to 2480 parts of the elasticized epoxy resin according to Example 3a) (75% solution) and the mixture is heated to 100 ° C. for 2 hours. The epoxy value then fell to 0. 100 parts of water are then added at 120 ° C. for the hydrolysis of the ketimine. The mixture is distilled, if appropriate with the addition of further water, until no more methyl isobutyl ketone passes over. The residue is then diluted with isobutanol to a solids content of 65%.

Höpler-Viskosität (50%ig in Ethylenglykolmonobutylether bei 20°C): 4700 mPa.sHöpler viscosity (50% in ethylene glycol monobutyl ether at 20 ° C): 4700 mPa.s

d) Herstellung des organisch gelösten Einbrennlacksd) Production of the organically dissolved stoving lacquer

In einer Mischung aus 1065 Teilen des Epoxid/Amin_Adduktes nach Beispiel 3c), 600 Teilen des Umsetzungsproduktes nach Beispiel 1b), 20 Teilen Dibutylzinndilaurat und 350 Teilen Ethylenglykolmonoethylether wird eine Mischung aus 891 Teilen Titandioxid und 9 Teilen Russ angeteigt und in einer Rührwerksmühle mit 2000 Teilen Glasperlen (Durchmesser: 2 mm) vermahlen, bis eine Körnigkeit nach DIN 53203 von ca. 10 µm erreicht ist. Der nach Abtrennen der Mahlkörper erhaltene 65%ige Lack wird in einer Nassfilmdicke von 100 µm auf Stahlbleche gerakelt und 20 Minuten bei 160°C eingebrannt. Die erhaltenen Filme zeigen nach 50 maligem Hin- und Herreiben mit einem mit Methylisobutylketon getränkten Wattebausch keinen Angriff.In a mixture of 1065 parts of the epoxy / amine adduct according to Example 3c), 600 parts of the reaction product according to Example 1b), 20 parts of dibutyltin dilaurate and 350 parts of ethylene glycol monoethyl ether, a mixture of 891 parts of titanium dioxide and 9 parts of carbon black is pasted and mixed in a stirrer mill with 2000 parts Grind glass beads (diameter: 2 mm) until a granularity according to DIN 53203 of approx. 10 µm is reached. The 65% lacquer obtained after separating off the grinding media is knife-coated onto steel sheets in a wet film thickness of 100 μm and baked at 160 ° C. for 20 minutes. The films obtained show no attack after rubbing back and forth 50 times with a cotton ball soaked in methyl isobutyl ketone.

Schichtdicke: 25 µmLayer thickness: 25 µm

Glanz ≮ 60°: 86%Gloss ≮ 60 °: 86%

Pendelhärte nach König: 178 secPendulum hardness according to König: 178 sec

Erichsen-Tiefung: 6,5 mmErichsen cupping: 6.5 mm

Claims (12)

1. A heat-curable surface-coating agent which contains, as binder, a mixture of
(A) from 1 to 90% by weight of a polyadduct, polycondensate or other polymer which has an average molecular weight M n of from 500 to 10,000 and, per molecule, on average two or more OH or primary or secondary amino groups, or two or more OH, primary and secondary aminogroups, or two or more OH and primary or secondary amino groups, or two or more primary and secondary amino groups, and
(B) from 99 to 10% by weight of a reaction product of
(a) one or more polyamines which on average contain two or more primary amino groups per molecule, with or without hydroxyl groups, and
(b) from 75 to 200 mole %, based on the primary amino groups of component (a), of one or more cyclic carbonic acid esters of the formula (I)
Figure imgb0006
 where R¹, R², R³ and R⁴ are identical or different and each is hydrogen, methyl or ethyl with the proviso that at least two radicals are methyl and/or ethyl.
2. A surface-coating agent as claimed in claim 1, which contains a polyester as component (A).
3. A surface-coating agent as claimed in claim 1, which contains a polyacrylate as component (A).
4. A surface-coating agent as claimed in claim 1, which contains, as component (A), a polyadduct which carries basic nitrogen groups and, bonded to aromatic rings, groups of the formula (II)
Figure imgb0007
 where R⁵ and R⁶ are identical or different and each is hydrogen or methyl.
5. A surface-coating agent as claimed in claim 1, which contains, as component (A), a reaction product of phenolic Mannich bases and epoxy resins.
6. A surface-coating agent as claimed in claim 1, which contains, as component (A), a reaction product of one or more aromatic or aliphatic epoxy resins and one or more primary or secondary amines.
7. A surface-coating agent as claimed in any of the preceding claims, which is water-dilutable on partial or complete neutralization with an acid.
8. The use of a surface-coating agent as claimed in claim 1, 2, 3 or 6 as a constituent of organically dissolved baking finishes.
9. The use of a surface-coating agent as claimed in claim 1, 2, 3 or 6 for powder coating.
10. The use of a surface-coating agent as claimed in claim 7 for preparing cathodically depositable electropaints.
11. The use as claimed in claim 8, 9 or 10, wherein a catalytically active amount of one or more catalysts is present.
12. An aqueous cathodic electrocoating bath which contains 5-30% by weight of a surface-coating agent as claimed in claim 7.
EP84103141A 1983-03-30 1984-03-22 Heat-curable coating composition and its use Expired - Lifetime EP0120466B2 (en)

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DE3460255D1 (en) 1986-07-31
US4543376A (en) 1985-09-24
EP0120466B1 (en) 1986-06-25
EP0120466A1 (en) 1984-10-03
DE3311518A1 (en) 1984-10-04
ATE20532T1 (en) 1986-07-15

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